Separating hydrated phosphorus pentoxide



2 Sheets-Sheet l W. H. BASKERVILL SEPARATING HYDRATED lPHOSPHORUS PENTOXIDE Filed Sept. 3, 1940 Dec. 1, 1942.

W w y WT .N HE mv .aN W/l W ATTORNEY 2 sheets-sheet 2 w. H. BASKERVILL Filed Sept. 5, 1940 Dec. l, 1942..

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Patented Dec. l, 1942 UNITED STAT las PATENT ori-"ica sEPARA'rmG' mmRA'rEn Pnosrrrorws PEN'roxmE wimam n. askerviu, Knoxville, 'remil Application september 3, 1940, serial No. 355,177

(ci. 231s5 (Granted under the act oiPMarch 3, 1883, as

amended April 30, '1928; 370 0 G. 757) 7 Claims.

The invention herein describedmay be manufactured yand used by or for the Government for governmental purposes without the payment to me of any royalty thereon.

This invention relates to the art of making phosphoric acid from elemental phosphorus, par- .ticularly the separation of hydrated Phosphorus pentoxide obtained after oxidizing elemental phosphorus.

After elemental phosphorus has been oxidized with air to form phosphorus'pentoxide and the phosphorus pentoxide has been hydrated, it is well known that various phosphoric acids, which are hydrates of phosphorus pentoxide, may be formed depending upon the conditions of temv -packed columns, withl or without recirculation of contact liquid. The prior art contains several proposals to this eilect, but from all information available no such proposal has been either in plant size operations or effective in obtaining any substantial removal of hydrated .phosphorus pentoxide in operations on any scale whatsoever.

The hydrated phosphorus pentoxide requiring separation occurs as a dispersoid in the hot gaseous mixture containing the same and not as a true gas. For this reason, electrical precipitation has hitherto been found to be the only effective method for obtaining'substantial separation of such hydrated phosphorus pentoxide, in spite of relatively high cost of installation and operation and relatively low capacity of the apparatus re quired.

I have discovered av process for separating vhy- I drated phosphorus pentoxide from phosphorus combustion products by passing said combustion products upwardly thru a packed separating column. by cooling the top of vsaid column sufficiently to provide' a contact liquid over said packing, by maintaining the flow of said combustion products thru said column at a velocity such that said column is maintained just below its loading or flooding point, by regulating the temperature of said combustion products entering said column to a temperature required for the production of a phosphoric acid of the character in which said hydrated phosphorus pentoxide is separated, and by withdrawing said phosphoric acid from near the bottom of said column. In this manner substantiallyall of the hydrated pentoxide contained in such combustion products may be separated as a phosphoric acid which is one of the hydrates of phosphorus pentoxide or as a mixture of such acids.

` In the accompanying drawings which form a part of the 'specicatiom Fig. 1 is a diagrammatical, vertical, sectional Iview of one form of apparatus for the embodiment of my invention.

Fig. 2 shows the percent of hydrated phosphorus pentoxide recoveredas a function of the velocity of the combustion products carrying such phosphorus pentoxide thru a packedI separating column. v

Fig. 3 shows the percent of hydrated phosphorus pentoxide recovered as a function of the v depth of packing thru which combustion products carrying such phosphorus pentoxide passes thru a separating column packed with one-inch- Raschig rings.

Fig. 4 shows the percent of hydrated phosphorus pentoxide recovered as' a function of the pressure drop of the combustion products containing such phosphorus pentoxide in passing thru a packed separating column.

In Fig. 1 elemental phosphorus thru valved w line l and compressed air thru valved line 3 are delivered to burner 5. 'I'he atomized phosphorus together with primary air supplied to burner E thru conduit 'i is delivered into vaporizing cham' ber d to produce primary combustion products containing elemental and oxidized phosphorus.

When crude phosphorus is used, fused-solventimpurities may be withdrawn from time to time from vaporizingv chamber 9 thru outlet `l I. The primary combustion productsv from vaporizing chamber s are discharged thru conduit I8 into burner it into combustion chamber il. Secondary air for completing the oxidation of phosphorus in the primary combustion products -is supplied to burner l5 thru conduit I9. Aqueous liquid for hydrating the phosphorus pentoxide in the combustion products in chamber il `and partially cooling the same is admitted to said chamber thru a plurality of valved 'inlets represented by valved inlet-rl. since some liquid and` a trace of solid impurities may from time to lating the temperature of the combustion products passing into the bottom of packed column 21 `thru control oi the aqueous liquid admitted thru the valved inlets 2l to a temperature required for theproduction of any particular phosphoric acid, as will hereinafter be described in more detail, such phosphoric acid is produced in column 21 and is withdrawn therefrom thru outlet 3|. The velocity oi' the phosphorus combustion products passing countercurrent to the contact liquid in the packed column 21 is so regulated that the column is maintained just below its loading or ooding point. The residual combustion products reaching the top of column 21 pass thru conduit 33 and are partially cooled by aqueous liquid dispersed therein from valved inlet 31 and pass into condenser 35 to which sumcient cooling iluid is provided to condense only a portion of the water vapor carried in such products around any of the dispersed hydrated phosphorus pentl oxide which is contained therein and which has proper velocity of combustion products thrupacked column 21. The dilute phosphoric acid from separator 39 passes into receiver 45 from which it is withdrawn as required thru valved -line 41 to pump 49 which discharges thru valved line 5| either to dilute phosphoric acid storage 53 or thru valved line 55 thru which it passes to one or more of inlets 31, 29, and 2l.

One example of the operation of the present invention is given for the continuous separation o! hydrated phosphorus pentoxide as ortho-phosphoric acid from hot partially cooled elemental phosphorus combustion products in a senil-plant scale apparatus, substantially as shown m Fig. l. provided with a separating column packed with one-inch Raschig rings to a height oi 18 feet. The hot combustion products, containing 2.29 pounds of P205 per mci. and cooled to 542 F. (283 C.) were admitted tothe bottom of the column and passed therethru at an average velocity of '7.2 feet per second, which was sumcient to maintain said column just below its loading or ilooding point in respect to the contact liquid drawn from the bottom of the column.V The eectiveness of the present process for separating hydrated phosphorus pentoxide is shown by comparingthe results of the above operation with those obtained by the previous operation of the same apparatus in a manner disclosed in the prior art, namely, by operating the packed co!- umn as a gas absorption unit. In that operation the hot combustion productsv containing 2.01 lbs. of P205 per mcf. and cooled to 447 F. (230 C.) were admitted to the bottom of the column and passed therethru at an average velocity of 2.1 ft.

' per second which is of theorder of gas velocities required in gas absorption practice but substantially below the velocity required to maintain the column in a loaded or flooded condition. The

-temperature at top of the column was F.

(57 CJ. A recovery of 41.3% of hydrated phosphorus pentoxide was obtained in the packed separating column in the form of orthophosphoric acid containing 83.1% by weight of HaPOi which was withdrawn from the bottom of the column. Furthermore, the eiectiveness of the.

present process for separating hydrated phosphorus pentoxide is shown by comparing the results of the operation, according to the first example, by the previous operation of the same apparatus in the manner disclosed in the prior art, f

locity of 2.8 ft. per second and 84 lbs. per minute of orthophosphoric acid, containing 90.5% by weight 0f HaPOi, was admitted to near the top of said column to provide the contact liquid over the packing therein. The temperature at the top ofthe column was 157 F. (69 C.). No recovery of any of the hydrated phosphorus pentoxide was obtained in the packed separating column.

A second example of the operation of the present invention is given for the continuous separation of hydrated phosphorus pentoxide as orthophosphoric acid from hot partially cooled elemental phosphorus combustion products in a plant scale apparatus, as shown in Fig. 1, provided with a separating column packed with oneinch Raschig rings to a height of 21 feet. The hot combustion products cooled to 500 F. (260 C.) were admitted to the bottom of the column and passed therethru at a velocity such as to maintain said column just below its loading or flooding point in respect to the contact liquid therein. The vapor leaving the top of the column at a temperature of F. (74 C.), containing a very small proportion of the total hydrated phosphorus pentoxide which was admitted to the bottom of the column, was cooled sufficiently to condense only a small portion of the water vapor contained therein around the remaining hydrated phosphorus pentoxide to form dilute orthophosphoric acid. This dilute phosphoric acid was separated and admitted to near the top of the column to provide the small amount of Water required to maintain the proper amount of contact liquid within the column. A recovery of 99.1% of the hydrated phosphorus pentoxide was,

obtained in the form o! orthophosphoric acid containing '12% by weight of HaPOg which was withdrawn from the` bottom of the column. Similarly, effective separation has been obtained in plant scale apparatus using a separating column packed with 2 to 6 inch mesh coke also operated under conditions such that the column was just below its loading or ilooding point. During plant scale operations covering a period of 24 months in which elemental phosphorus was burned at a rate of approximately 1000 pounds per hour, four test studies were made each test lasting approximately oneweek. The concentration of orthophosphoric acid produced during each test period was approximately 80% by weight of H3PO4 and the overall recoveries of phosphorus pentoxide during the respective test periods were as follows: 99.89%, 99.98%, 99.98% and 99.94%,

The third example of the operation of the present invention is given for the continuous separation of hydrated phosphorus pentoxide as metaphosphoric acid from hot partially cooled elemental phosphorus combustion products in another semi-plant scale apparatus, as shown in Fig. 1, provided with a separating column packed with 1/2 inch Raschig rings to a height of 10 feet. The hot combustion products cooled to 1380 F. (749 C.) were admitted to the bottom of the column at an average velocity of 6.6 feet per second which was sumcient to maintain said column just below its loading or flooding point. A recovery of 86% of the hydrated phosphorus pentoxide was obtained in the packed separating column in the form of metaphosphoric acid which was withy drawn from the bottom of the column. The same a study of each set of raw materials and the lntermediate and finished products involved.

'The elemental phosphorus is oxidized to phosphorus pentoxide with at least a suflicient quanti- 'the hot gaseous 'mixture may be materially reapparatus has also been operated to separatethe duced by the presence of this excess air. However, inthe operation of the present process, it is preferred to use a' minimum amount of excess air since the required cooling of the hot gaseous mixture is more satisfactorily accomplished by the use of water or other suitable aqueous iiuid temperature in the combustion and hydration phosphoric acid and pyrophosphoric acid. While g the temperature of the hot combustion products entering the bottom of the packed separating column are required to be cooled to about 1380 F. (749 C.) for the production of metaphosphoric acid, these hot combustion products are required to be cooled to about 1100 F. (593` C.) for the production of tetraphosphoric acid and further .I

cooled to a temperature of about 840 F. (449 C.) for the production of pyrophosphoric acid.

A summary of the resultsl obtained ln numerous semi-plant scale and plant scale operations showing the recovery of hydrated phosphorus pentoxide as a function of the velocity of combustion products carrying such phosphorus pentoxide through a packed separating column, as a function of the depth of the packing through which the combustion products carrying -such -phosphorus pentoxide passes through such a separating column, and as a function of the pressure drop of the combustion products carrying such phosphorus pentoxide passing through such sparating column is shown in Table 1.

chamber. The temperature to which the hot gaseous mixture is cooled depends upon a number of factors, the more important of which are: the acid, or mixture of acids, which are to vbe produced; the amount and character of the cooling liquid which is to be used subsequently in maintaining a proper temperature at the'point of separation oi the acid; and the time of subsequent contact with the contact liquid descending counter-current to the flow of the partially cooled gaseous mixture. In any event, the hot gaseous mixture is generally cooled to a temperature at least slightly above the temperature of TABLE 1.-Separating hydrated phosphorus penioande zn packed columns as orthophosphorzc acid Gas temperature Column gas velocities Packing o Pressure Acid con- F it' Sec' drop ,P205 fr contra- AP, coutent, er Genf tion,

Hel ht Ave inches lbs./M ft.a p R per cent Kind ,t gh inlet ourlet Bottom 'rop u water Haro,

Rings 1". 9 546 158 8. 1 5. 9 7. 0 8.4 2. 38 75. 2 81.0 Rings l" 13. 5 545 152 8. 3 5. 9 7.1 13. 6 2.51 90.0 82. 0 Rings 1". 18 447 135 2. 5 1. 7 2. 1 0. 8 2. 01 41. 3 83.1 Rings 1". 18 444 130 5. 4 4.1 4. 7 8. 7 2. 15 71. 0 84. 9 Rings 1". 18 446 150 6. 8 5. 2 6. 0 10. 9 2. 17 84. 6 86. 3 Rings l". 18 540 145 8. 5 6. 0 l 7. 2 15. 0 2. 3F 92. 8 81. 5 Rings l". 18 542 145 8.5 6. 0 7. 2 17. 6 2. 29 94. 2 81.0 Rings l" l 21 500 165 2l. 5 99.1 72.0 Coke 18 444 150 4.4 3. 5 3. 9 3. 8 2. 13 67. 3 86. 6 Coke 4". 18 432 110 2. 8 15. 7 2. 00 96. 0 80. 0 Coke 2-6" l 17 530 170 11. 4 95. 7 80. 8

i Plant scale apparatus. It is evident that there are numerous factors which will influence conditions for the most satisfactory operation oi this invention, the actual water vapor in thepartially cooled gaseous mix-l ture will, therefore, substantially depend upon the amount of 'water which is required forgthe limits of which cannot be established except by 75 `partial cooling of such mixture.

Since the partially cooled mixture containing dispersed hydrated phosphorus pentoxide is separated mechanically in the packed separating column, the mechanism by which such dispersed particles are collected is considered to be a series of mechanical impingements, or small-angle centrifugal eiects. On this basis the separating or centrifugal force is proportional to the square of the velocity of the gaseous mixture passing through the packed column. The effectiveness of separation, therefore, increases substantially with the increase in .velocity of the gaseous mixture passing upwardly through the packed separating column up to the point where said column reaches a loaded or flooded condition. The loading or flooding point of a packed column is the gas velocity upward through such column at which the liquid passing down therethrough starts to be carried out of the column with the gas leaving the packing. Therefore, the critical .condition for the operation of the packed separ-v ating column is to operate with a gas velocity such that the column i's maintained at just below its loading or flooding pint. In operations involving the use of separating columns packed with one-inch Raschig rings, it has been found that a gas velocity of the order'of 8 to 10 ft. per second is most satisfactory for this purpose. Such operation is in contra-distinction with the general practice used in the operation of socalle locity is in the order of a 2 ft. per second. Since thegas velocity through a packed column will vary depending upon'the character of the packing, it is standard practice to define this velocity absorption column in which the gas veon the basis of the cross section of the empty e column. A specified gas velocity for one particular packing will not necessarily be the same for some other packing but there is anequivalent gas velocity for such other packing by which the same eect is produced. Using packing material of a pre-formed or molded type the velocity of -gas through the packing is not generally susceptible to material change as long as the packing remains in its original condition. Howeverfusing` packing material of irregular size and shape, such as coke, gradual rearrangement or disintegration of some of the packing will necessarily change the characteristicsof the column. There.. fore, as a practical matter in plant operation it is generally preferred to observe the conditions the column to orthophosphoric acid at the top of) of operation insofar as the approach to the loadv ing or flooding point is concerned by regulating the pressure drop through the packing material.

A pressure drop through the packed separating columnof the order of 15 to 20 inches of water is generally satisfactory for control of the column lust below itsloading or flooding point.

In order that a packed separating column may function satisfactorily an adequate supply of conpoint I.

through the packed'separating column and in F18. 3 showing the recovery of hydrated phosphorus pentoxide as a function of the height of packing in such a column, curve 2 is a plot of equation which represents the recovery of. a dispersiod by a series-of mechanical irnpingernents wherein R is the percentage of hydrated phosphorus pentoxide recovered in the column, e is the base oi' the natural system of logarithme, h is the height in feet of one-inch Raschig rings packing, and u" is the average velocity of the elemental phosphoruswherein R is the percentage of hydrated phosphorus pentoxide recovered in the column, e is the ba'se of the natural system oflogarithms, and AP is the pressure drop of gas through the column in inches of water. The values obtained in semi-plant scale operation's using one-inch Raschig rings to a-height of 18 vfeet are likewise shown by a plurality of points represented by The` values obtained in senil-plant scale operations using the same packing but .varying lthe height of the packing is shown by a plurality of points` represented by point 8 and resulting from semi-plant scaleoperations as a 3/4 inch coke packing to a hei of 18 feet is shown by pointl. The results f plant scale operations obtained in plant scale operations using one-inch Raschig rings to a height of 21 feet is shown by point i2, and the results of plant lscale operations using 2 to 6 inch coke packing to a height of 17 feet is shown by point l 4.

The composition of the acid in the column may vary from metaphosphoric acid at the bottom of the column, depending, of course, upon the time of contact of the gasand liquid in the column and the temperature maintained at the bottom of vthe column. With indirect cooling, some of the metaphosphoric acid in the partially cooled mixture successfully further hydrates to tetraphosphoric acid, pyrophosphoric acid and orthophostact liquid must bel provided over the packing material. In the 'present process the hot gaseous mixture from which the hydrated phosphorus pentoxide is being separated always vcontains a substantial quantity of water vapor. One method of supplying contact liquid is to cool the top of the separating column sumciently to condense a portion of the water vapor contained thereinand thereby supply contact liquid in thev top of the column. In plant scale operations, however,

it is preferable to supply a regulated amount of .V aqueous liquid to the top of the column to maintain the required amount o! contact liquid. In Fig. 2 showing the recovery of hydrated phosphorus pentoxide as a function of a gas velocity phoricv acid.` With these respective acids, or mixtures of the same, being separated from the mixture as it passes progressively `upward thru the column, theortho'phosphoric acid separating in the top of the column is then successfully dehydrated thru pyrophosphoric acid, tetraphosphoric acid and metaphosphoric acid where the proper conditions are so maintained. Likewise, in the production of other acids, thedehydration will `proceed only to the extent required for the respective conditions which are maintained. When itis desired to maintain a definite temperature gradient in' the column, direct cooling may be aifected by admitting water or other4 suitable aqueous nuid into the column at the top and/or var- 'io'us elevations in regulated quantities. '.Such direct increase the time of contact required by the sas and'liquid in the column and increase the temperature required for. the gaseous mixture admitted thru the bottom of the column. The temperature which is to be maintained at the bottom of the column depends primarily upon the acid or mixture of acids which are being produced and the time of contact between the gas and liquid in the column required for such production. The actual temperature required is determined by the partial pressure of the water vapor in the partially cooled gaseous mixture entering the column, the gas velocity 'thru the column, the amount and character of the cooling agent admitted to the column, if the latter is used, and theproper design of the column. It will be seen, therefore, that the higher the partial pressure of the water vapor in the gaseous mixture entering the column and the greater the amount of'cooling liquid entering the column, the higher the gas temperature will be required in the bottom of the column. The examples give a general indication of the magnitude of the temperature at the bottom of the column for the production 'of the respective individual acids. Likewise, mixtures of at least two individual phosphoric acids may be produced by properly regulating the temperature in the bottom of the column or dilute orthophosphoric acid may be so produced.-

The temperature at the top of the packed co1- umn is preferably maintained at slightly above the dew point of the gaseous mixture leaving the column. The temperature atl the top of the column may, however, be carried at a somewhat higher temperature, in which case it may be desirable to pass the gaseous mixture thru a condenser in winch at least a part of the water vapor contained in the hot gaseous mixture is condensed and the small proportion of orthophosphorio acid carried in such mixtures separated out with condensed' water. 4is an aqueous fluid of suitable character to be used either in the hydration of the phosphorus pentoxide to metaphosphoric acid and thepartial cooling of the hot gaseous mixture or in the direct cooling of the packed column.

The following terms mean and include: phosphoric acid refers to metaphosphoric acid, tetraphosphoric acid, pyrophosphoric acid, orthophosphoric acid, or mixtures of the same, or dilute orthophosphoric acid,in fact, phosphoric acid is used and refers to any of the phorus 'produced or combination aqueous iluid,"

. to the hydration of phosphorus pentoxide to metaphosphoric acid and cooling the hot gaseous 'mixture either prior to or after the packed column. refers to water, pl'ciisphoric acid, or any other suitable aqueous fl d.

It will'be seen, therefore, that tually may be carried out by the use of various modifications and changes without departing from its spirit or scope, with only such limitations placed thereon as may be imposed by the prior art.

Thisapplication is a continuation-impart of my application Serial No. 192,742, iiled February I claim:

l. A process phorus-pentoxide from phosphorus combusti products containing water vapor in excess of that required to hydrate the phosphorus pentoxide thereof; and

for separating hydrated phos- This dilute orthophosphoric. acidhydrates of phosproduction as used specifically in reference therein whichcomprises (a) passing said combustion products upwardly thru a packed sepa- (b) cooling the top of said column su-iiiciently to provide a contact liquid over said packing, (c) lmaintaining the ilow of said combustion products thru said column at a velocity such that said column is maintained iust'below its loading or flooding temperature'of said combustion products entering said column to a temperature required for the concentration of phosphorus (e) withdrawing said phosphoric predetermined pentoxide, and

2. The processaccording to claim 1 wherein (a) an aqueous liquid is admitted to near the top of said packed separating column in an amount required to provide sufficient contact liquid to maintain said column just below its loading or flooding point.

top of said packed separating column in an amount required to provide suilicient contact liquid to maintain said column just below its loading or flooding point, and (b) an aqueous liquid is dispersed in said combustion products containing hydrated phosphorus pentoxide in an amount sufcient to regulate said combustion products entering said column to the temperature required for the production oi a owable phosphoric acid of a predetermined concentration of phosphorus pentoxide.

4. The process according to claim 1 wherein (a) the gaseous mixture from which most of the phosphorus pentoxide has been separated in said colunm is cooled suiliciently to condense a portion of the watervapor therein together with substantially all .of the remainder of the hy drated phosphorus pentoxide to form a' oondensate of dilute aqueous'solution or orthophosphoric acid, and (b) --sald condensate is admitted to near the top of said column to provide cooling therein,

5. The process according to claim 1 wherein (a) the gaseous mixture from which most o! the phosphorus pentoxide' has been separated in said column is cooled suiliciently to condense a portion therein, and (c) is dispersed in said combustion products to pro vide in .part the regulation of the temperature of ond to maintain said products entering said column.

- 6. The process v(a) said combustion products are passed upwardly thru said column packed with one-inch to 10 iee't per secbelow'its loading or flooding point.

'I-..The process according to claim 1 .wherein (a) .said column packed with one-inch Raschig rings is maintained Just below its loading 01:'

drop o wmwm n. Basknnvmn point, (d) regulating the I of a flowable phosphoric acidoi a according to claim 1 wherein 1 y CERTIFIGATE oF CQRRECTION, Patent No. 2,505,518. December '1 lghz'. l i wILLnm H'. BAsKERvIm'..

It is hereoy certifiedthat'erro'r appears in the 'printed specification of the above numbered patent reqiring correction as follows: Page li, first column, line: 214., for "pintf 1'e1el'. l .,point'; line 52, for *of'a 2" read.

5.5 and 61, for' fsuccessfully" read successirely; nd that the said Letters Patent should be read with :this corection 'therein that the same may conform tothe record of, the cose in the Patent Office. signed and sealed this ,121:11 day of January, A. D. 19M.

. Henry Van Arsdale, (Seal) Acting 'Commissioner of Patents. 

